JPS61173935A - Refractory silicone group laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a fire-resistant silicone-based laminate. Specifically, the present invention relates to a fire-resistant silicone-based laminate called vf@, in which a glass mat layer is integrally laminated on a fire-resistant sheet having a flame-retardant silicone layer formed on the surface of an inorganic fiber cloth.

[Prior art 1] Conventionally, spark-blocking sheets are known in which a silicone rubber layer is laminated on stainless steel cloth or glass cloth (Japanese Unexamined Patent Publication No. 52-24904, ¥tNWg 55-14
64798). A fire-resistant sheet is known that is made by laminating a silicone resin layer on mata and gaumata cloth (Japanese Patent Laid-Open No. 5
4-68470). Furthermore, an insulating base material is known in which a silicone resin layer is laminated on glass cloth, asbestos cloth, etc., and a silicone rubber layer is integrally laminated on the silicone resin layer (Japanese Patent Application Laid-open No. 32082/1982).
.

However, although sheets made of stainless steel cloth or glass cloth laminated with a silicone rubber layer have the ability to block welding sparks, they have the disadvantage that the silicone rubber burns when exposed to flame. The same applies to sheets in which a silicone resin layer is laminated on glass cloth, asbestos cloth, etc., and a silicone rubber layer is laminated thereon.

Furthermore, a fire-resistant sheet made by laminating a flame-retardant silicone resin layer on a glass cloth has excellent fire resistance, but has a drawback in that it cannot sufficiently block out high heat generated from flames etc. due to insufficient heat insulation. This invention was made in view of the above-mentioned drawbacks of the prior art, and its purpose is to provide a material that can withstand exposure to flame for a considerable period of time, and that An object of the present invention is to provide a laminate mainly made of silicone that can block heat.

[Means for solving the problem 1 This objective is achieved by laminating and integrating a glass mat layer on one side of a fire-resistant sheet in which a flame-retardant silicone layer is formed on at least one side of an inorganic fiber cloth. be done.

Here, the flame-retardant silicone layer may be formed on only one side of the teamless cloth, or may be formed on both sides. From the viewpoint of preventing fraying of the inorganic fiber cloth and improving fire resistance, it is preferable to form it on both sides. Further, when forming the flame-retardant silicone layer on only one side, it is preferable to form the fire-retardant silicone layer on the other side, which has 11 glass mat layers, from the viewpoint of improving fire resistance.

Examples of the inorganic fiber cloth include nonflammable and heat resistant materials such as glass fiber, asbestos, rock wool, carbon fiber, silicon carbide fiber, and stainless steel fiber. In addition, in terms of form, woven fabrics, knitted fabrics,
Nonwoven fabrics are exemplified. It may be a blend or blend of different types of fibers.

The flame-retardant silicone for the flame-retardant silicone layer may be silicone rubber, silicone resin, or an intermediate between silicone rubber and silicone resin, as long as it has a thickness of 0.16 mm and passes UL standard v-i, preferably v-0. The curing PIi structure may be an addition reaction curing type, a condensation reaction curing type, an organic peroxide curing type, etc.-1
゜In the case of silicone rubber, in addition to platinum fine powder or platinum compound, aluminum hydroxide powder, carbon platter, mica, 7
It is often found in those containing one or more of titanium oxide, aluminum oxide powder, zinc oxide powder, potassium titanate fiber, zinc carbonate powder, manganese carbonate powder, etc.

The same applies to silicone resins and materials intermediate between silicone rubber and silicone resins.

Glass mats include glass fiber covered strand mats and plus wool mats.

The thickness under no load is 0.5 mm or more for glass chopped strand mats and 1 mm for glass wool mats.
．． 5 mm or more is preferable.

Even if the glass mat layer is laminated and integrated with the flame-retardant silicone rubber layer formed on the inorganic fiber cloth directly or via a silicone adhesive layer, it does not form the flame-retardant silicone layer of the inorganic fiber cloth. They may be integrally laminated on one side with a silicone adhesive layer interposed therebetween.

The silicone adhesive for this purpose may be room temperature curing type or heat curing type, rubber type or resin type, as long as it has adhesive strength by containing an adhesion promoter, but it is preferably flame retardant. .

[Function 1] In the silicone-based laminate of the present invention, the inorganic fiber cloth acts as a core material, reinforcing the flame-retardant silicone layer and blocking flames. The flame-retardant silicone layer acts as a flame barrier. A fire-resistant sheet with a flame-retardant silicone layer formed on at least one side of an inorganic fiber cloth is used to reinforce the mat layer, facilitate handling, and prevent flames from directly hitting the glass mat layer. .

The glass mat layer functions to shield heat from flames or high-temperature heating elements and to moderate physical impact.

[Example 1] This invention will be explained by an example. "Example Middle" means parts by weight. Viscosity is the value at 25°C. The load thickness of the glass wool mat was measured using a dialage thickness meter model H manufactured by Ozaki Seisakusho.

The fire resistance of the silicone-based laminate test piece and comparative test piece was measured under the following conditions. Inner diameter of tube9. 4++I11, height 1
A standard gas (methane, hydrogen) is discharged from a 01.6mm Bunsen burner and ignited, and the height of the blue flame is 45mm.
It was adjusted to

140mm x 1 with a 65mm diameter hole in the center
A 10 mm metal (thickness: 3 ml11) test specimen stand was mounted at a height of 30 mm from the upper end of the Bunsen burner using another stand.

Place a test specimen cut into a size of 140mm +
．． A polyethylene disk of 95-1.05+++ m was placed. Note that the silicone-based laminate and the fire-resistant sheet with a flame-retardant silicone layer formed only on one side were placed so that the flame-retardant silicone layer was exposed to flame.

The time was measured from the moment the Bunsen burner flame was vertically applied to the bottom center of the test specimen, and at the same time, a propane gas flame with an inner diameter of 3III11 and a flame height of 20I was brought into contact with the surface of the polyethylene disk every 5 seconds. As a result, the time required for the polyethylene disk to ignite was determined as the ignition time in units of 5 seconds.

Example 1 ° Flat t-shirt with a thickness of 0.25 mm! jL is on both sides of Lascross, 100 parts of dimethylpolysiloxane end-blocked with vinyl groups at both ends with a viscosity of 100ocs, 1.0 part of methylhydrodiene polysiloxane with a viscosity of 40CS, and a platinum compound catalyst as main ingredients, and 0.11 part of benzotriazole to delay the addition reaction. A light gray paste-like addition reaction curable silicone rubber composition containing 1.0 part of carbon black as an agent and 50 parts of aluminum hydroxide powder as a flammability improver was coated by the knife-to-ter method and heated at 170°C for 50 parts. By press vulcanizing for a minute, each side has a thickness of 0.
A fire-resistant sheet having a flame-retardant silicone rubber layer formed thereon was obtained.

The flame retardancy of this flame retardant silicone rubber itself is 0.
．． It passed UL94V-0 at 16mm.

A paste-like two-component dealcolation condensation reaction-curable flame-retardant silicone rubber adhesive (flame-retardant 20ppn+ as platinum as an improver
chloroplatinic acid, 1.0% by weight of carbon black, 35% by weight of aluminum hydroxide, and 1.8% by weight of γ-7 minopropyltrimethoxysilane as an adhesion promoter) to improve the fire resistance. Heat to 25℃ while pressing on one side of the sheet.
By holding for a certain period of time, a glass wool mat layer is laminated and integrated on one side of the plain weave lath cloth with flame-retardant silicone rubber layers formed on both sides via a flame-retardant silicone rubber adhesive layer, as shown in Figure 1. A silicone-based laminate was obtained. The fire resistance of these samples was as follows.

Ignition time: Silicone laminate (invention) 11 minutes 20 seconds Fire-resistant sheet (comparative example) 40 seconds is Rustool Mat (
Comparative Example) 3 minutes 35 seconds Example 2 The addition reaction curable silicone rubber composition used in Example 1 was coated on one side of a flat Ik7y lath cloth with a thickness of 0.35+ nm using a knife coater, and the mixture was heated in an atmosphere of 170°C for 5 minutes. By holding for a minute, one side will have a thickness of 0.
A fire-resistant sheet on which a 15 mm layer of 11 flammable silicone rubber was formed was obtained.

Although the silicone rubber layer of this fire-resistant sheet is not formed, an oxime-free one-component room-temperature curing flame-retardant silicone rubber adhesive (same retardant as the flame-retardant silicone rubber adhesive of Example 1) is applied to the lacrosse surface. (containing a flammability improver and an adhesion promoter) was applied thereon, and the lath wool mat used in Example 1 was left in contact with the lath wool mat under pressure and left open for 24 hours in the air at 30"C. A silicone-based laminate was obtained in which a fire-resistant sheet with a fire-resistant silicone rubber layer formed on one side was integrated with a glass mat layer laminated on the other side via a silicone rubber adhesive layer.The fire resistance of these samples was It was as follows.

Ignition time silicone laminate (invention) 11 minutes 5 seconds Fire-resistant sheet (comparative example) 40 seconds Glass wool mat (comparative example) 3 minutes 35 seconds Example 3 Methylphenyl poly with silanol group content of 1.4% by weight Silicone varnish LO consisting of 50% by weight of siloxane resin and 50% by weight of xylene.

To this part, 12 parts of methyltrimethoxysilane and 1.5 parts of tetrabutyl titanate were added as a hardening agent, 20 parts of mica was added as a flame retardant improver, and 15 ppm of chloroplatinic acid was added as a platinum, and the mixture was well mixed to form a paste. Thickness: 1.
A fire-resistant flame-resistant silicone resin layer with a thickness of 0.1ml11 is formed on one side by spreading it on one side of 2n++a asbestos cloth using the knife coater method, air-drying it, and holding it in hot air at 200°C for 10 minutes. (The flame retardance of this flame retardant silicone resin itself is 0 when the thickness is 0.
16n+mUL94V-0 passed). The flame-retardant silicone rubber adhesive used in Example 2 was spread on the side of the above-mentioned fire-resistant sheet on which the flame-retardant silicone resin layer was not formed using a knife coater method, and the no-load thickness was 2. 0mm, load thickness 11.0mm was pressed against a lath wool mat (single fiber diameter 9μ) at 30'C for 24 hours.
By standing for a period of time, a silicone-based laminate was obtained in which a fire-resistant silicone resin layer was formed on one side of the asbestos cloth and a glass mat layer was laminated and integrated on the other side.

The fire resistance of these samples was as follows.

Ignition time: Silicone-based laminate (invention) 9 minutes 50 seconds Fire-resistant sheet (comparative example) 1 minute 20 seconds is Ruswool mat (
Comparative example) 2 minutes 10 seconds Example 4 Dimethylsiloxane/methylvinylsiloxane copolymer (molar ratio of both units 0.14:99.86) Raw rubber 100
A silicone rubber composition consisting of 40 parts of hydrophobized silica having a BET surface area of 170 m2/g was mixed with 30 ppm of platinum weight of chloroplatinic acid, 40 parts of aluminum hydroxide powder, 10 parts of mica powder, and 1.5 parts of ci'cumyl peroxide.
0.6m thick by calembling method.
Coated on both sides of n+ glass cloth (the flame retardance of this silicone rubber itself is UL9 at a thickness of 0°16 mm).
It passed 4V-0). The thickness of each silicone rubber layer was 0.6 mm.

On one side, the unloaded thickness is 1.01, and the loaded thickness is 0°9m11.
By placing the glass chopped strand mat of No. 1 on the table, squeezing it with a calendar, and vulcanizing it in hot air at 250'C for 10 minutes, a fire-resistant silicone rubber layer is formed on both sides of the lath cloth in the shape of 7> as shown in Fig. 2. A silicone-based laminate was obtained in which a glass chopped land mat layer was directly laminated and integrated on one side of the silicone-based laminate. The fire resistance of these samples was as follows.

Ignition time: Silicone-based laminate (invention) 3 minutes and 50 seconds Fire-resistant sheet (comparative example) 50 seconds Glass chopped strand mat (comparative example) 45 seconds [Effect 1 The silicone-based laminate of this invention has no 8! A glass mat layer is integrally laminated on either side of a fire-resistant sheet with a flame-retardant silicone layer formed on at least one side of the fiber cloth, so that flame or high-temperature heating elements and flammable articles or melting point or softening If the fire-resistant sheet layer faces the flame or high-temperature heating element and the plus mat layer faces or touches the article between the article and the article that does not have a high point, the combustion and melting of the article can be significantly delayed. can. Moreover, the article can be effectively protected from physical impact.

Therefore, it is useful as a fireproof coating material for communication/control cables, optical communication fiber cables, etc., a material for firefighting suits, a fireproof coating material near blast furnaces, steelmaking furnaces, and lath kettles, and a scattering shielding material for high-temperature molten materials.

[Brief explanation of drawings]

FIG. 1 is a sectional view of the silicone-based laminate of Example 1, and FIG. 2 is a sectional view of the silicone-based laminate of Example 4. 1a...Glass wool mat 1b...Glass chopped strand mat 2...Flame retardant silicone rubber adhesive 3...Glass cloth 4...Flame retardant silicone rubber patent applicant Toray Silicone Co., Ltd. Hiraoka Textile Co., Ltd.

Claims (1)

[Claims] 1. A fire-resistant silicone, characterized in that a glass mat layer is laminated and integrated on one side of a fire-resistant sheet made of an inorganic fiber cloth with a flame-retardant silicone layer formed on at least one side. system laminate. 2. The silicone-based laminate according to claim 1, wherein a glass mat layer is integrally laminated on one side of a fire-resistant sheet made of an inorganic fiber cloth with flame-retardant silicone layers formed on both sides. 3 A glass mat layer is laminated and integrated with a flame-retardant silicone adhesive layer on the side on which the flame-retardant silicone layer is not formed of a fire-resistant sheet with a flame-retardant silicone layer formed on one side of an inorganic fiber cloth. A silicone-based laminate according to claim 1. 4. The silicone-based laminate according to claim 1, wherein the flame-retardant silicone layer is a flame-retardant silicone rubber layer or a flame-retardant silicone resin layer.